CN108288702B - Preparation and application of sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyaniline multilevel structure material - Google Patents
Preparation and application of sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyaniline multilevel structure material Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 76
- 244000198134 Agave sisalana Species 0.000 title claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 48
- 239000002135 nanosheet Substances 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 41
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 39
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 34
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 24
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- YNNGZCVDIREDDK-UHFFFAOYSA-N aminocarbamodithioic acid Chemical compound NNC(S)=S YNNGZCVDIREDDK-UHFFFAOYSA-N 0.000 claims description 7
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- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 30
- 239000010406 cathode material Substances 0.000 abstract description 12
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- 239000011889 copper foil Substances 0.000 description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000003610 charcoal Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The invention discloses a preparation method and application of a sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyaniline multilevel structure material. The sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyaniline multilevel structural material is structurally characterized in that the sisal fiber-based three-dimensional carbon nanosheet is used as a framework, flower-shaped molybdenum disulfide grows on the framework, and the conductive polyaniline is uniformly coated on the surfaces of the sisal fiber-based three-dimensional carbon nanosheet and the molybdenum disulfide. The preparation method comprises the following steps: (1) preparing a sisal fiber-based three-dimensional carbon nanosheet; (2) preparing a solution; (3) carrying out hydrothermal reaction; (4) heat treatment; (5) and coating the conductive polyaniline. The invention has the advantages of wide raw material source, low price, easily controlled process conditions, strong operability and good repeatability; the prepared sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyaniline multilevel structure material is stable in structure and good in conductivity. When the material is used as a lithium ion battery cathode material, the material has high reversible capacity, excellent rate capability and cycling stability.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery electrode materials, and particularly relates to a preparation method of a sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyaniline multilevel structure material and application thereof in a lithium ion battery.
Background
The lithium ion battery has the advantages of light weight, long cycle life, no memory effect, low self-discharge efficiency, small environmental pollution and the like, so that the lithium ion battery is widely applied to the fields of mobile electronic equipment, national defense industry and the like. However, with the rapid development of electric vehicles and large-scale energy storage devices, the market places higher demands on the performance of lithium ion batteries. The cathode material is used as an important component of the lithium ion battery and plays a key role in the performance of the lithium ion battery. The theoretical specific capacity of the traditional graphite negative electrode material is 372 mAh/g, and the requirement of a new generation of high-performance lithium ion battery negative electrode material cannot be met. Therefore, there is an urgent need to develop a lithium ion negative electrode material having high performance.
The biomass charcoal, especially the biomass charcoal with a two-dimensional structure, generally has a rich pore structure, a large specific surface area and good electrical conductivity, and the characteristics enable the biomass charcoal as a lithium ion battery negative electrode material to show high specific capacity, superior rate capability and cycling stability. In addition, as a renewable resource, the biomass charcoal also has the advantages of environmental protection and low price. Therefore, many biomass charcoals are considered to be used as lithium ion battery negative electrode materials, such as rice hull charcoal, peanut hull charcoal, straw charcoal and the like. Sisal hemp is used as a crop with perennial heat zone hard leaf fibers, is widely planted in Guangxi, has rich and easily obtained fiber yield, is natural and porous, is easy to activate, and can be used as a raw material of a lithium ion battery cathode material. However, in practical application, sisal fiber carbon still has low coulombic efficiency for the first time and reversible capacity which cannot meet the development requirements of the times, and modification of the sisal fiber carbon is considered to be a feasible way.
Molybdenum disulfide (MoS)2) As a conventional transition metal sulfide, it is considered as one of the most potential lithium ion battery negative electrode materials because it has a high lithium storage capacity (670 mAh/g specific capacity is stored per 4mol of lithium consumed) and a low price. MoS2Can be divided into single-layer and multi-layer, single-layer MoS2The structure of a sandwich-like structure is formed by an upper S atom layer and a lower S atom layer and a middle Mo atom layer, the layers are combined by weak van der Waals force, the structure is very suitable for the intercalation and deintercalation of lithium ions, and MoS is generated in the reaction process of the battery2Can also be converted into metal Mo and L iS2This further increases the lithium storage capacity of the electrode, and these properties contribute to the MoS2Becomes a potential lithium storage material with high energy density. However, MoS when used as a lithium ion battery negative electrode2There are also some problems: MoS of single or several layers2The nanosheets are very easy to agglomerate, and L iS formed in the conversion process2Easily react with electrolyte to form a very thick sol polymer film; the volume change is large in the process of lithium ion intercalation and deintercalation, so that the electrode is easy to pulverize and damage; the conductivity is low, resulting in poor rate performance. These problems greatly limit MoS2The lithium ion battery is widely applied to the aspect of lithium ion batteries.
Polyaniline is considered as the most promising conductive polymer material due to its easy synthesis, low cost and stable structure. The polyaniline is used for modifying the surface of the cathode material, which is an important method for improving the electrochemical performance of the cathode material. The surface of the negative electrode material is coated with a layer of polyaniline to form a core-shell structure, and the constituent materials of the structure can form a synergistic effect, so that the performances of the constituent materials are improved, such as better conductivity, shorter ion transmission channel, better structural stability, lower specific surface area to reduce the occurrence of side reactions, and the like.
The invention leads MoS to be subjected to a hydrothermal method2Growing on a sisal fiber base three-dimensional carbon nano-sheet, coating a layer of conductive polyaniline on the surface by an in-situ oxidation polymerization method, and preparing the sisal fiber base three-dimensional carbon nano-sheet/MoS with special structure and morphology2The polyaniline multi-level structure material has excellent electrochemical performance when being used as a lithium ion battery cathode material. And the lithium ion battery cathode material with the multilevel structure and the preparation method thereof are not reported.
Disclosure of Invention
The invention aims to provide a preparation method of a sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyaniline multilevel structure material and application thereof in a lithium ion battery, aiming at the defects of the prior art.
The structural characteristics of the sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyaniline multi-level structure material are as follows: the sisal fiber-based three-dimensional carbon nanosheet is used as a framework, the flower-shaped molybdenum disulfide grows on the framework, and the surfaces of the sisal fiber-based three-dimensional carbon nanosheet and the molybdenum disulfide are uniformly coated with the conductive polyaniline. When the multi-level structure material is used as a lithium ion battery cathode, excellent rate capability and cycling stability are shown, and the specific capacity of 583mAh/g is still kept after 400 times of cycling under the current density of 2A/g.
The preparation method of the sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyaniline multilevel structure material comprises the following specific steps:
(1) weighing 3-5 g of cleaned and dried sisal fibers, putting the cleaned and dried sisal fibers into a polytetrafluoroethylene inner container of a 100m L hydrothermal reaction kettle, adding a strong base solution with the concentration of 70m L of 1.5-2.5 mol/L, covering a steel shell, screwing, putting into a constant-temperature oven, heating at the constant temperature of 160 ℃ for 14 hours, naturally cooling, taking out solid substances in the inner container, washing the solid substances to be neutral by deionized water, and putting into a constant-temperature blast oven to perform drying treatment at the constant temperature of 60 ℃ for 12 hours to obtain dry white flocculent single fibers.
(2) Weighing 4.5-7.5 g of solid KOH, preparing a solution by using 150m L deionized water, adding 3g of the single fibers obtained in the step (1), quickly stirring for 60 minutes under an electric stirrer, and drying in a forced air oven at a constant temperature of 80 ℃ until water is completely evaporated to obtain a mixture of the KOH and the single fibers.
(3) And (3) putting the mixture of the KOH and the single fibers obtained in the step (2) into a tubular atmosphere furnace, heating to 400-500 ℃ at a heating rate of 2-3 ℃/min under the protection of nitrogen at a flow rate of 40-50 m L/min, preserving heat for 3 hours, heating to 800-850 ℃ at a heating rate of 2-3 ℃/min, preserving heat for 1 hour, naturally cooling, taking out, grinding and pulverizing in an agate mortar, washing with sufficient hydrochloric acid with a concentration of 3 mol/L for 1 time, washing with deionized water to be neutral, and then putting into a constant-temperature blast oven to perform drying treatment at 60 ℃ to obtain the sisal fiber-based three-dimensional carbon nanosheet (refer to Chinese patent with application number of 201710125304.4, namely sisal fiber-based nitrogen and sulfur co-doped graphene carbon material and preparation method).
(4) Preparing a solution: 0.1g of sisal fiber-based three-dimensional carbon nanosheet obtained in the step (3), and 0.02-0.08 g of molybdenum trioxide (MoO)3) And 0.08 to 0.015g of ammonium dithiocarbamate (CH)6N2S2) Adding the mixture into 70m L deionized water, and quickly stirring the mixture for 20 to 30 minutes on a magnetic stirrer, wherein the mixed solution is marked as A mixed solution.
(5) Hydrothermal reaction: and transferring the mixed solution A into a stainless steel reaction kettle, reacting for 12-36 hours at 120-180 ℃, filtering out a black product after the reaction is finished, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying in a blast oven at 80 ℃ to obtain a product B.
(6) Thermal treatmentPutting the product B into a tubular atmosphere furnace, and feeding N with the flow rate of 40-50 m L/min2Raising the temperature from normal temperature to 800 ℃ at the speed of 1-3 ℃/min under protection, carrying out heat treatment by a heating program with the heat preservation time of 1 hour, and taking out the product after natural cooling to obtain a product C.
(7) Coating conductive polyaniline, namely weighing 50mg of product C, putting the product C into a three-neck flask, and adding 70m of H with L concentration of 0.5-2 mol/L2SO4Magnetically stirring the solution for 15 minutes to disperse the product C, then adding 0.015-0.06 m L analytically pure aniline, magnetically stirring for 2 hours, then weighing 0.0375-0.075 g of ammonium persulfate and dissolving the ammonium persulfate in 10m L H with the concentration of 0.5-2 mol/L2SO4And slowly dripping the solution into the system, stirring the solution at 25 ℃ for 12 hours, filtering out a green product, washing the green product with deionized water and absolute ethyl alcohol for three times respectively, and drying the product in a vacuum drying oven at 60 ℃ for 10 hours to obtain the sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyphenyl multilevel structure material.
(8) Manufacturing a pole piece: and (3) weighing the cathode material obtained in the step (5), acetylene black and polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, adding N-methyl pyrrolidone (NMP) as a solvent, stirring until uniform slurry with moderate viscosity is formed, uniformly coating the slurry on a copper foil with the thickness of 5-20 microns, placing the copper foil in a forced air drying oven for drying at a constant temperature of 60 ℃ for 10 hours, and then placing the copper foil in a vacuum drying oven for drying at a constant temperature of 110 ℃ for 12 hours. And taking out after naturally cooling to normal temperature, and punching into a wafer with the diameter of 16mm by using a punching machine.
(9) And (3) assembling the battery, namely taking a lithium sheet as a reference electrode and a counter electrode, taking the round pole piece obtained in the step (8) as a working electrode, taking a microporous polypropylene membrane as a diaphragm, and using L iPF of 1 mol/L6EC (ethylene carbonate) + DMC (dimethyl carbonate) + DEC (diethyl carbonate) as electrolyte (L iPF in electrolyte)6As solute, the volume ratio of the solvent EC + DMC + DEC is 1:1:1), and the L IR2025 type button half-cell is assembled in a glove box filled with high-purity argon and sealed.
(10) And (3) testing the battery: and (4) placing the assembled battery in the step (9) for 12 hours and then carrying out electrochemical test. The cycle test of the experimental lithium ion battery is completed on a battery tester (BTS-10mA, Shenzhen New Wildlike technology Limited) at room temperature, and the voltage range is 0.01-3V.
The strong base is one of lithium hydroxide (L iOH), sodium hydroxide (NaOH), and potassium hydroxide (KOH).
The invention has the beneficial technical effects that: the method takes sisal fiber-based three-dimensional carbon nanosheets as a framework, and makes flower-shaped MoS by using a hydrothermal method2Growing on the surface of the skeleton, and coating a layer of elastic conductive polymer polyaniline on the surface of the skeleton. Wherein the sisal fiber-based three-dimensional carbon nanosheet framework can promote flower-shaped nano MoS2The dispersion of (2) and the provision of a conductive network, facilitate the rapid movement of electrons; flower-like MoS2A high specific capacity can be provided; the elastic conductive polyaniline coating layer on the surface can bear larger stress expansion, so that the volume change of the negative electrode material is relieved, the side reaction of electrolyte on the surface of the negative electrode material body is inhibited, and meanwhile, the conductivity of the coating layer can further provide a conductive network to be beneficial to the rapid movement of electrons. Due to the structural design, when the multi-level structural material is used as a lithium ion battery cathode material, the multi-level structural material has higher specific capacity, superior rate capability and cycling stability. When the current density is 0.1A/g, the reversible capacity reaches 684mAh/g, and even under the current density of 2A/g, the reversible capacity can be kept 583mAh/g after 400 cycles.
Drawings
FIG. 1 shows sisal fiber-based three-dimensional carbon nanosheets/MoS in example 2 of the present invention2Scanning electron microscope and transmission electron microscope images of the polyaniline multi-stage structure material.
In the figure: (a) (b) is a scanning electron micrograph, and (c) (d) is a transmission electron micrograph.
FIG. 2 shows sisal fiber-based three-dimensional carbon nanosheets/MoS in example 2 of the present invention2X-ray powder diffraction pattern of polyaniline multilevel structure material.
FIG. 3 shows sisal fiber-based three-dimensional carbon nanosheets/MoS in example 2 of the present invention2The multiplying power performance curve chart of the polyaniline multi-stage structure material as the lithium ion battery cathode material.
FIG. 4 shows sisal fiber-based three-dimensional carbon nanosheets/MoS in example 2 of the present invention2PolyanilineAnd (3) a cycle performance curve diagram of the multi-stage structure material as the lithium ion battery cathode material.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the scope of the invention.
Example 1:
(1) weighing 3g of cleaned and dried sisal fibers, putting the weighed sisal fibers into a polytetrafluoroethylene inner container of a 100m L hydrothermal reaction kettle, adding 70m L NaOH solution with the concentration of 1.5 mol/L, sleeving a steel shell, screwing, putting into a constant-temperature oven, heating at the constant temperature of 160 ℃ for 14 hours, naturally cooling, taking out solid substances in the inner container, washing the solid substances to be neutral by deionized water, and putting into a constant-temperature blast oven to be dried for 12 hours at the constant temperature of 60 ℃ to obtain dried white flocculent single fibers.
(2) Weighing 4.5g of solid KOH and preparing a solution by using 150m L of deionized water, adding 3g of the single fibers obtained in the step (1), quickly stirring for 60 minutes under an electric stirrer, and placing the mixture into a forced air oven to dry at constant temperature of 80 ℃ until water is completely evaporated to obtain a mixture of the KOH and the single fibers.
(3) And (3) putting the mixture of the KOH and the single fibers obtained in the step (2) into a tubular atmosphere furnace, heating to 400 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen at a flow rate of 40m L/min, preserving heat for 3 hours, then heating to 800 ℃ at a heating rate of 2 ℃/min, preserving heat for 1 hour, naturally cooling, taking out, grinding and pulverizing in an agate mortar, washing with sufficient hydrochloric acid with a concentration of 3 mol/L for 1 time, washing with deionized water to be neutral, and then putting into a constant-temperature air-blowing oven for drying treatment at 60 ℃ to obtain the sisal fiber-based three-dimensional carbon nanosheets (refer to the Chinese patent with the application number of 201710125304.4, namely sisal fiber-based nitrogen and sulfur co-doped graphene carbon materials and the preparation method).
(4) Preparing a solution: 0.1g of sisal fiber-based three-dimensional carbon nanosheet obtained in the step (3) and 0.02g of molybdenum trioxide (MoO)3) And 0.08g ammonium dithiocarbamate (CH)6N2S2) Added to 70m L of deionized water,the mixture was stirred rapidly on a magnetic stirrer for 20 minutes and was designated as mixture A.
(5) Hydrothermal reaction: transferring the mixed solution A into a stainless steel reaction kettle, reacting for 12 hours at 120 ℃, filtering out a black product after the reaction is finished, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying in a blast oven at 80 ℃ to obtain a product B.
(6) Heat treatment, the product B is put into a tubular atmosphere furnace and N with the flow rate of 40m L/min2Heating from normal temperature to 800 ℃ at the speed of 1 ℃/min under protection, carrying out heat treatment by a heating program with heat preservation for 1 hour, and taking out after natural cooling to obtain a product C.
(7) Coating conductive polyaniline, weighing 50mg of product C, placing into a three-neck flask, adding 70m of H with L concentration of 0.5 mol/L2SO4The solution was magnetically stirred for 15 minutes to disperse product C, 0.015m L of analytically pure aniline was added, and after 2 hours of magnetic stirring, 0.0375g of ammonium persulfate was weighed and dissolved in 10m L of 0.5 mol/L H2SO4And slowly dripping the solution into the system, stirring the solution at 25 ℃ for 12 hours, filtering out a green product, washing the green product with deionized water and absolute ethyl alcohol for three times respectively, and drying the product in a vacuum drying oven at 60 ℃ for 10 hours to obtain the sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyphenyl multilevel structure material.
(8) Manufacturing a pole piece: and (3) weighing the negative electrode material obtained in the step (7), acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, adding N-methyl pyrrolidone (NMP) as a solvent, stirring until uniform slurry with moderate viscosity is formed, uniformly coating the slurry on a copper foil with the thickness of 5 mu m, placing the copper foil in a forced air drying oven for drying at the constant temperature of 60 ℃ for 10 hours, and then placing the copper foil in a vacuum drying oven for drying at the constant temperature of 110 ℃ for 12 hours. And taking out after naturally cooling to normal temperature, and punching into a wafer with the diameter of 16mm by using a punching machine.
(9) And (3) assembling the battery, namely taking a lithium sheet as a reference electrode and a counter electrode, taking the round pole piece obtained in the step (8) as a working electrode, taking a microporous polypropylene membrane as a diaphragm, and using L iPF of 1 mol/L6EC (ethylene carbonate) + DMC (dimethyl carbonate) + DEC (diethyl carbonate) as electrolyte (L iPF in electrolyte)6As solute, the solvents EC + DMC + DEC in a volume ratio of 1:1:1), assembling L IR2025 type button half cells in a glove box filled with high-purity argon, and sealing.
(10) And (3) testing the battery: and (4) placing the assembled battery in the step (9) for 12 hours and then carrying out electrochemical test. The cycle test of the experimental lithium ion battery is completed on a battery tester (BTS-10mA, Shenzhen New Wildlike technology Limited) at room temperature, and the voltage range is 0.01-3V.
The obtained sisal fiber-based three-dimensional carbon nano sheet/MoS2The polyaniline multi-stage structure material grows a small amount of MoS on a sisal fiber-based three-dimensional carbon nanosheet framework2And the surface is coated with conductive polyaniline. When the material is used as a lithium ion battery cathode material, the reversible capacity is stabilized at 495mAh/g after 30 times of circulation under the current density of 500 mA/g.
Example 2:
(1) weighing 5g of cleaned and dried sisal fibers, putting the weighed sisal fibers into a polytetrafluoroethylene inner container of a 100m L hydrothermal reaction kettle, adding a KOH solution with the concentration of 70m L being 2.5 mol/L, sleeving a steel shell, screwing, putting into a constant-temperature oven, heating at the constant temperature of 160 ℃ for 14 hours, naturally cooling, taking out solid substances in the inner container, washing the solid substances to be neutral by deionized water, and putting into a constant-temperature blast oven to perform drying treatment at the constant temperature of 60 ℃ for 12 hours to obtain dried white flocculent single fibers.
(2) Weighing 7.5g of solid KOH and preparing a solution by using 150m L of deionized water, adding 3g of the single fibers obtained in the step (1), quickly stirring for 60 minutes under an electric stirrer, and placing the mixture into a forced air oven to dry at constant temperature of 80 ℃ until water is completely evaporated to obtain a mixture of the KOH and the single fibers.
(3) And (3) putting the mixture of the KOH and the single fibers obtained in the step (2) into a tubular atmosphere furnace, heating to 500 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen at a flow rate of 50m L/min, preserving heat for 3 hours, heating to 850 ℃ at a heating rate of 3 ℃/min, preserving heat for 1 hour, naturally cooling, taking out, grinding and pulverizing in an agate mortar, washing with sufficient 3 mol/L hydrochloric acid for 1 time, washing with deionized water to be neutral, and then putting into a constant-temperature air-blowing oven to perform drying treatment at 60 ℃ to obtain the sisal fiber-based three-dimensional carbon nanosheet.
(4) Preparing a solution: 0.1g of sisal fiber-based three-dimensional carbon nanosheet obtained in step (3), and 0.08g of molybdenum trioxide (MoO)3) And 0.015g ammonium dithiocarbamate (CH)6N2S2) Add to 70m L deionized water and stir rapidly on a magnetic stirrer for 30 minutes, and this mixture is denoted as a mixture.
(5) Hydrothermal reaction: and transferring the mixed solution A into a stainless steel reaction kettle to react for 36 hours at 180 ℃, filtering out a black product after the reaction is finished, washing the black product for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying the black product in a blast oven at 80 ℃ to obtain a product B.
(6) Heat treatment, namely putting the product B into a tubular atmosphere furnace and putting the product B into the tubular atmosphere furnace at the flow speed of 50m L/min of N2Heating from normal temperature to 800 ℃ at the speed of 3 ℃/min under protection, preserving heat for 1 hour, carrying out heat treatment, and taking out after natural cooling to obtain a product C.
(7) Coating conductive polyaniline, weighing 50mg of product C, placing into a three-neck flask, adding H with the concentration of 70m L being 2 mol/L2SO4The solution was stirred magnetically for 15 minutes to disperse product C, 0.06m L of analytically pure aniline was added and after 2 hours of magnetic stirring, 0.075g of ammonium persulfate was weighed and dissolved in 10m L of 2 mol/L of H2SO4And slowly dripping the solution into the system, stirring the solution at 25 ℃ for 12 hours, filtering out a green product, washing the green product with deionized water and absolute ethyl alcohol for three times respectively, and drying the product in a vacuum drying oven at 60 ℃ for 10 hours to obtain the sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyaniline multilevel structure material.
(8) Manufacturing a pole piece: carrying out the sisal fiber-based three-dimensional carbon nano sheet/MoS obtained in the step (7)2Weighing the polyaniline multilevel structure material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, adding N-methyl pyrrolidone (NMP) as a solvent, stirring until uniform slurry with moderate viscosity is formed, uniformly coating the slurry on a copper foil with the thickness of 5-20 mu m, placing the copper foil in a forced air drying oven for drying at the constant temperature of 60 ℃ for 10 hours, and then placing the copper foil in a vacuum drying oven for drying at the constant temperature of 110 ℃ for 12 hours. Naturally cooling toTaking out the wafer after normal temperature, and punching the wafer into a wafer with the diameter of 16mm by using a punching machine.
(9) And (3) assembling the battery, namely taking a lithium sheet as a reference electrode and a counter electrode, taking the round pole piece obtained in the step (8) as a working electrode, taking a microporous polypropylene membrane as a diaphragm, and using L iPF of 1 mol/L6EC (ethylene carbonate) + DMC (dimethyl carbonate) + DEC (diethyl carbonate) as electrolyte (L iPF in electrolyte)6As solute, the volume ratio of the solvent EC + DMC + DEC is 1:1:1), and the L IR2025 type button half-cell is assembled in a glove box filled with high-purity argon and sealed.
(10) And (3) testing the battery: and (4) placing the assembled battery in the step (9) for 12 hours and then carrying out electrochemical test. The cycle test of the experimental lithium ion battery is completed on a battery tester (BTS-10mA, Shenzhen New Wildlike technology Limited) at room temperature, and the voltage range is 0.01-3V.
Subjecting the obtained sisal fiber-based three-dimensional carbon nano sheet/MoS2The polyaniline multilevel structure material is used for carrying out appearance and structure characterization. The material can be seen from a scanning electron microscope (figure 1 (a)) picture, is a multi-stage structural material, and the conductive polyaniline coated on the surface can be seen through magnified observation (figure 1 (b)); from the transmission electron microscope picture (FIG. 1 (c)) it can be seen that the material as a whole exhibits a transparent state, indicating that the material as a whole is thin, while from the high-resolution transmission electron microscope picture (FIG. 1 (d)) it can be seen that the crystal planes with interplanar spacings of 0.27nm, 0.22nm and 0.18nm, respectively, correspond to MoS2The (100), (103), (105) crystal plane (JCPDS No. 75-1539); without MoS observed2The (002) crystal face of (A) is caused by the coating of conductive polyaniline. The diffraction peaks of 3 materials contained in the material can be seen from the X-ray powder diffraction curve (figure 2), wherein the diffraction peaks at 14.12 degrees, 32.92 degrees and 58.76 degrees respectively correspond to MoS2The (002), (100) and (110) crystal planes of (A); the broad peak at about 24 degrees is a diffraction peak belonging to sisal fiber-based three-dimensional carbon nano-sheets; while the peaks at 20 ° and 25 ° belong to the diffraction peaks of the (020) and (200) crystal planes of the conductive polyaniline; these results indicate that this material is a composite material consisting of 3 relatively pure phases.
Subjecting the obtained sisal fibers toWiki three-dimensional carbon nano sheet/MoS2The polyaniline multilevel structure material is used for carrying out electrochemical performance characterization. From the rate performance curve (fig. 3), it can be seen that when the current density is 0.1, 0.3, 0.5, 1.0, 2.0, 3.0 and 5.0A/g, respectively, the reversible capacity of the electrode is 673, 626, 579, 534, 451, 406 and 349mAh/g, respectively, and when the current density returns to 0.1A/g again, the reversible capacity also returns to 684mAh/g, indicating that the material has better rate performance and cycling stability. From the constant current charge and discharge curve (fig. 4), it can be seen that the reversible capacity is maintained at 583mAh/g after 400 cycles at a current density of 2A/g.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those of ordinary skill in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (1)
1. A sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyaniline multi-level structure material is characterized in that the sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyaniline multi-level structure material has the structure: the sisal fiber-based three-dimensional carbon nanosheet is used as a framework, flower-shaped molybdenum disulfide grows on the framework, and the surfaces of the sisal fiber-based three-dimensional carbon nanosheet and the molybdenum disulfide are uniformly coated with the conductive polyaniline;
the preparation method of the sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyaniline multilevel structure material comprises the following specific steps:
(1) preparing a solution: 0.1g of sisal fiber-based three-dimensional carbon nanosheet and 0.02-0.08 g of MoO3Adding 0.08-0.015 g of ammonium dithiocarbamate into 70m L deionized water, and rapidly stirring for 20-30 minutes on a magnetic stirrer, wherein the mixed solution is marked as A mixed solution;
(2) hydrothermal reaction: transferring the mixed solution A into a stainless steel reaction kettle, reacting for 12-36 hours at 120-180 ℃, filtering out a black product after the reaction is finished, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying in a blast oven at 80 ℃ to obtain a product B;
(3) and (3) performing heat treatment, namely putting the product B into a tubular atmosphere furnace, and performing N treatment at the flow speed of 40-50 m L/min2Raising the temperature from normal temperature to 800 ℃ at the speed of 1-3 ℃/min under protection, carrying out heat treatment by a heating program with the heat preservation time of 1 hour, and taking out after natural cooling to obtain a product C;
(4) coating conductive polyaniline, namely weighing 50mg of product C, putting the product C into a three-neck flask, and adding 70m of H with L concentration of 0.5-2 mol/L2SO4Magnetically stirring the solution for 15 minutes to disperse the product C, then adding 0.015-0.06 m L analytically pure aniline, magnetically stirring for 2 hours, then weighing 0.0375-0.075 g of ammonium persulfate and dissolving the ammonium persulfate in 10m L H with the concentration of 0.5-2 mol/L2SO4Slowly dripping the solution into the system, stirring the solution at 25 ℃ for 12 hours, filtering out a green product, washing the green product with deionized water and absolute ethyl alcohol for three times respectively, and drying the product in a vacuum drying oven at 60 ℃ for 10 hours to obtain a sisal fiber-based three-dimensional carbon nanosheet/molybdenum disulfide/polyphenyl multilevel structure material;
the preparation method of the sisal fiber-based three-dimensional carbon nanosheet in the step (1) comprises the following steps:
①, weighing 3-5 g of cleaned and dried sisal fibers, putting the weighed sisal fibers into a polytetrafluoroethylene inner container of a 100m L hydrothermal reaction kettle, adding 70m L of strong base solution with the concentration of 1.5-2.5 mol/L, sleeving a steel shell, screwing, putting into a constant-temperature oven, heating at the constant temperature of 160 ℃ for 14 hours, naturally cooling, taking out solid substances in the inner container, washing the solid substances to be neutral by deionized water, putting into a constant-temperature blast oven, and drying at the constant temperature of 60 ℃ for 12 hours to obtain dry white flocculent single fibers;
②, weighing 4.5-7.5 g of solid KOH, preparing a solution by using 150m L deionized water, adding 3g of the ① single fibers, quickly stirring for 60 minutes under an electric stirrer, and drying in a forced air oven at a constant temperature of 80 ℃ until water is completely evaporated to obtain a mixture of the KOH and the single fibers;
③, putting the mixture of the KOH obtained in the step ② and single fibers into a tubular atmosphere furnace, heating to 400-500 ℃ at a heating rate of 2-3 ℃/min under the protection of nitrogen at a flow rate of 40-50 m L/min, preserving heat for 3 hours, then heating to 800-850 ℃ at a heating rate of 2-3 ℃/min, preserving heat for 1 hour, naturally cooling, taking out, grinding and pulverizing in an agate mortar, washing with sufficient hydrochloric acid with a concentration of 3 mol/L for 1 time, washing with deionized water to be neutral, and then putting into a constant-temperature blast oven to perform drying treatment at 60 ℃ to obtain sisal fiber-based three-dimensional carbon nanosheets;
the strong base is one of L iOH, NaOH and KOH.
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Application publication date: 20180717 Assignee: Guilin Rongjia Environmental Protection Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980045322 Denomination of invention: Preparation and Application of Sisal Fiber Based 3D Carbon Nanosheets/Molybdenum Disulfide/Polyaniline Multilevel Structural Materials Granted publication date: 20200731 License type: Common License Record date: 20231103 |
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